Finishing agents and method of manufacturing the same

ABSTRACT

An ultra-thin, water- and oil-repelling and durable overcoat easily formed on a substrate surface via covalent bonding by applying a finishing agent, in which a chemical adsorbent including at least one chlorosilyl group is mixed in a nonaqueous viscous liquid or a solid medium, to the substrate surface; and an oil-repelling, extremely thin and durable overcoat with a high water-separation property covalently bonded to a substrate surface by applying an organsiloxane-based finishing agent, in which at least one organosiloxane bond chain and chlorosilyl group are mixed in a nonaqueous viscous liquid or a solid medium, to the substrate surface.

This is continuation-in-part of application Ser. No. 08/068661, filedMay 27, 1993.

FIELD OF THE INVENTION

The invention relates to a wax-type finishing agent and a method ofmanufacturing the same. More particularly, the invention relates to amethod of manufacturing a finishing agent to form a durable ultra thinwater- and oil-repelling chemically adsorbed overcoat on the surface ofa substrate. The invention also relates to a method of manufacturing awax-type organosiloxane-based finishing agent used for forming achemically adsorbed overcoat with a high water-separation property.

BACKGROUND OF THE INVENTION

Finishing agents have been used in many fields, such as automobile wax,floor and interior products, glazing agents, fur polish, lubricants fora papered sliding door or sliding paper door, and mechanical parts orthe like.

The above-noted conventional finishing agents are solid or emulsified,and generally comprise the mixture of a petroleum solvent, silicone, waxor lower alcohol, and an abrasive material.

Conventional finishing agents have weak water repelling and lusteringproperties, and conventional overcoats do not have sufficient enduranceand hardness since they are merely applied to the substrate surfaces. Inaddition, they hardly possess an oil-repelling property. Since theagents are physically adhered to the substrate surfaces, they haveendurance and solidity deficiencies.

SUMMARY OF THE INVENTION

An objective of the invention is to provide wax-type finishing agentswith superior water-repelling, lustering and water-separation propertiesand a method of manufacturing the same, wherein an overcoat chemicallybonded to a substrate surface has sufficient endurance and hardness, andwherein the overcoat with an oil-repelling property is formed on thesubstrate surface, thereby solving the above-noted problems.

In order to accomplish this and other objects and advantages, oneembodiment of the finishing agent of the invention comprises a siloxanecompound, a chemically adsorptive compound with at least one halosilylgroup, and a nonaqueous viscous liquid or a solid medium.

It is preferable in this composition that the siloxane compound is atleast one compound selected from the group consisting of Si(OH)₄,SiH(OH)₃, SiH₂ (OH)₂, and Si(OH)₃ O[Si(OH)₂ O]_(n) Si(OH)₃ (wherein n is0 or an integer).

It is also preferable in this composition that the chemically adsorptivecompound comprising at least one halosilyl group is provided as seenbelow:

    ASiX.sub.p Y.sub.3-p

wherein A represents an organic group containing at least one groupselected from the group consisting of an alkyl group, a vinyl group, anethynyl group, an aryl group, a silicon containing organic group and anoxygen containing organic group; X is a member selected from the groupconsisting of H, an alkyl group, an alkoxyl group, a fluoroalkyl groupand a fluoroalkoxyl group; Y represents at least one halogen groupselected from the group consisting of Cl, Br, F and I; and p represents0, 1 or 2.

It is preferable in this composition that the viscosity of thenonaqueous viscous liquid or solid medium is 1000 cps or above.

It is also preferable in this composition that the viscous liquid orsolid medium has a boiling point at 100° C. or above and is mixed withthe viscous liquid or solid medium having a boiling point from 25° C. to100° C.

It is preferable in this composition that the finishing agent comprisesinorganic particles having an average diameter less than 10 μm.

A method of manufacturing the finishing agent of the invention comprisesthe steps of:

adding a silyl compound comprising at least two halogen groups into amixture of a tertiary amine or amide with no active hydrogens and anonaqueous viscous liquid or solid medium;

reacting the silyl compound with water contained in the mixture, thusforming a siloxane compound; and

adding and mixing a chemically adsorptive compound comprising at leastone halosilyl group with the siloxane compound.

Active hydrogens are hydrogens which can promote a condensation reactionwith a halosilyl group of a halosilane compound. More specifically, suchhydrogens include --OH, --COOH, --CHO, --NH₂, >NH, and the like.

It is preferable in this method that the silyl compound comprising atleast two halogen groups is at least one compound selected from thegroup consisting of SiCl₄, SiHCl₃, SiH₂ Cl₂, and SiCl₃ O(SiCl₂ O)_(n)SiCl₃ (wherein n represents 0 or an integer).

Since the finishing agent of the invention contains the siloxanecompound, chemically adsorptive compound comprising at least onehalosilyl group, and nonaqueous viscous liquid or solid medium, theagent is a wax-type finishing agent with excellent water-repelling andlustering properties. An overcoat formed from the finishing agent of theinvention is chemically bonded to a substrate surface with sufficientendurance and hardness, and has oil-repelling properties. When thefinishing agent is rubbed and coated on a substrate surface like a carwax, an extremely thin and water- and oil-repellent overcoat withsignificant endurance is formed easily on the substrate surface. Thecoating procedures are also simple, and a large-scale reactor is notrequired in the invention.

If the siloxane compound is at least one compound selected from thegroup consisting of Si(OH)₄, SiH(OH)₃, SiH₂ (OH)₂, and Si(OH)₃ O[Si(OH)₂O]_(n) Si(OH)₃ (wherein n is 0 or an integer), the compound wouldprovide a lustering property to an overcoat. The siloxane compound isalso effective as an agent to control viscosity.

When the chemically adsorptive compound comprising at least onehalosilyl group is AsiX_(p) Y_(3-p) (wherein A represents an organicgroup containing at least one group selected from the group consistingof an alkyl group, a vinyl group, an ethynyl group, an aryl group, asilicon containing organic group and an oxygen containing organic group;X is a member selected from the group consisting of H, an alkyl group,an alkoxyl group, a fluoroalkyl group and a fluoroalkoxyl group; Yrepresents at least one halogen group selected from the group consistingof Cl, Br, F and I; and p represents 0, 1 or 2), an overcoat can bechemically adsorbed to a substrate surface via Si groups. The mostpreferable chemically adsorptive compound is a compound comprising achlorosilyl group.

Conveniently, the finishing agent is inhibited from running during itsapplication to a substrate surface when the viscosity of the viscousliquid or solid medium is 1000 cps or above. If the viscous liquid orsolid medium with its boiling point at 100° C. or above is mixed withone having its boiling point from room temperature to 100° C., anovercoat can firm up quickly right after the application of the agent byvaporizing the material with the lower boiling points. As a result, theremoval of the finishing agent is made simple.

Moreover, if an abrasive material, having particles less than 10 μm inaverage diameter (such as alumina, silicon carbide, boron carbide,chromium oxide, iron oxide, synthetic diamond or fine-grain silica) isadded to the finishing agent, a small amount of the substrate surface isremoved without reducing the luster of the surface. As a result, thereaction between the chemically adsorptive compound containing at leastone chlorosilyl group and the cleaned substrate surface is improved.

The method of manufacturing the finishing agent of the inventionincludes the steps of:

preparing a nonaqueous viscous liquid or solid medium:

adding and mixing a silyl compound comprising at least two halogens (forexample, Cl groups);

promoting a dehydrohalogenation (such as a dehydrochlorination reaction)between water contained in the viscous liquid or solid medium and thesilyl compound, thus generating a siloxane compound and dehydrating atthe same time; and

mixing a chemically adsorptive compound comprising at least onechlorosilyl group, thus keeping the chemically adsorptive compound in anactive condition.

It is preferable to use SiCl₄, SiHCl₃, SiH₂ Cl₂, or SiCl₃ O(SiCl₂ O)_(n)SiCl₃ (wherein n represents 0 or an integer) as the silyl compoundcomprising many Cl groups. The volume of the silyl compound added to theviscous liquid or solid medium is required to be enough to remove waterin the nonaqueous viscous liquid or solid medium.

The nonaqueous viscous liquid or the solid medium normally contains alittle water. Nonaqueous is defined as having a water content of 100 ppmor less. Therefore, when the chemically adsorptive compound comprisingat least one chlorosilyl group is directly added to the viscous liquidor solid medium, the compound would be reacted to water and thendeactivated. Thus, a tertiary amine or amide comprising no activehydrogens is mixed in the nonaqueous viscous liquid or solid medium, andthen a dehydrochlorination reaction between water contained in theviscous liquid or medium and thiol- or amino-based impurities isgenerated by mixing a material containing many chlorosilyl groups intothe liquid or medium mixed with the tertiary amine or amide, thusforming a siloxane compound. In other words, the water reacts withsiloxane, to form hydrochloric acid and promote dehydration. Thiol- oramino-base impurities react with SiCl groups, thereby forming Si S bondsor Si--N bonds and bonding to a polysiloxane compound.

The hydrochloric acid is vaporized and removed. It is not necessary toremove the polysiloxane compound since it is stable to the chemicallyadsorptive compound comprising at least one chlorosilyl group. Rather,the polysiloxane compound should not be removed because the compound canprovide a lustering property to an overcoat. Water contained in theviscous liquid or solid medium and thiol or amino-based impurities areremoved due to the dehydrochlorination reaction with the materialcontaining many chlorosilyl groups after adding a chemically adsorptivecompound comprising at least one chlorosilyl group. Thus, a finishingagent, in which the chemically adsorptive compound comprising at leastone chlorosilyl group is contained in an active condition, can bemanufactured.

Based on a method of using a finishing agent of the invention, theagent, comprising a chemically adsorptive compound with at least onechlorosilyl group and a nonaqueous viscous liquid or solid medium, isapplied to a substrate surface comprising hydrophilic groups. Then, thesubstrate surface is reacted with the compound comprising at least onechlorosilyl group. When active hydrogens are contained in the substratesurface, a dehydrochlorination reaction is generated between thechlorosilyl groups of the compound and the active hydrogens, therebyfixing molecules comprising at least one chlorosilyl group to thesubstrate surface by a covalent bonding via Si atoms. Unreactedfinishing agent is then either wiped off or washed away with detergentor water. Although the compound is very reactive to moisture in the air,the nonaqueous viscous liquid or solid medium can protect the substratesurface from moisture in the air, thereby helping to promote thedehydrochlorination reaction on the substrate surface.

Due to this method, an ultra-thin overcoat of molecules comprising atleast one chlorosilyl group is covalently bonded to the substratesurface via Si atoms.

As explained above, it is important to maintain the active condition ofthe chemically adsorptive compound comprising at least one chlorosilylgroup in the finishing agent. If the chemically adsorptive compoundmaintains its active condition, a condensation reaction is promotedbetween the compound and active hydrogens on a substrate surface. Inother words, the compound is not hydrolyzed when the compound maintainsits active condition.

When a fluorocarbon group is contained in a molecule comprising at leastone chlorosilyl group, a strong, water- and oil repelling fluorocarbonpolymer overcoat can be formed on a substrate surface. It is preferableto use CF₃ (CF₂)_(n) (R)_(m) SiX_(p) Cl_(3-p) (wherein n represents 0 oran integer, R represents an alkyl group, a vinyl group, an ethynylgroup, an aryl group or a substituent comprising a silicon atom or anoxygen atom; m represents 0 or 1; and X represents H, an alkyl group, analkoxyl group or a substituent comprising a fluoroalkyl group or afluoroalkoxy group; and p represents 0, 1 or 2) as the moleculecomprising at least one chlorosilyl group.

A substrate used in the invention which utilizes active hydrogens, maycomprise, for example, metals, ceramics, glass, plastic, paper, fiber,leather or the like. In case of plastic or fiber with no activehydrogens, the substrate surface can be made hydrophilic by treatment ina plasma or corona atmosphere containing oxygen.

Moreover, in order to prepare an organosiloxane-based finishing agentwhich can form an overcoat with a high water-separation property, acomposition containing a chemical adsorbent, comprising at least oneorganosiloxane bond chain and chlorosilyl group, and a nonaqueousviscous liquid or a solid medium is prepared.

If a material comprising at least one fluorocarbon chain and chlorosilylgroup is also added to the organosiloxane-based finishing agent, theagent can form an overcoat not only with a water-separation property butwith an oil-repelling property.

A method of manufacturing the organosiloxane-based finishing agentcomprises the steps of:

dehydrating a chemical adsorbent to around 10 ppm of water or less;

mixing the chemical adsorbent in an inactive nonaqueous viscous liquidor solid medium, thus preparing a mixture; and

adding a chemical adsorbent comprising at least one organosiloxane bondchain and chlorosilyl group into the mixture.

When the nonaqueous viscous liquid or solid medium is inactive, acondensation reaction is not promoted between the viscous liquid orsolid medium and the chemical adsorbent.

The chemical adsorbent comprising at least one organosiloxane bond chainand chlorosilyl group can be represented as R(SiR₂ O)_(n) SiCl₃ (whereinR represents an alkyl group and n represents an integer). Cl(SiR₂ O)_(n)SiR₂ Cl or Cl₃ SiO(SiR₂ O)_(n) SiCl₃ (wherein R represents an alkylgroup and n represents an integer).

When the material comprising at least one fluorocarbon chain andchlorosilyl group, CF₃ (CF₂)_(u) (R)_(m) SiX_(p) Cl_(3-p) (wherein m andn represent 0 or an integer; R represents an alkyl group, a vinyl group,an ethynyl group, an aryl group or a substituent comprising a siliconatom or an oxygen atom: X represents H, an alkyl group, an alkoxyl groupor a substituent comprising a fluoroalkyl group or a fluoroalkoxy group;and p represents 0, 1 or 2), is added to the organosiloxane-basedfinishing agent, an overcoat with high water-separation andoil-repelling properties can be formed.

If a tertiary amine or amide with no active hydrogens is also mixed inthe chemical adsorbent during the step of mixing the adsorbent in thenonaqueous viscous liquid or solid medium, an organosiloxane-basedfinishing agent with high stability is prepared.

A method of using the organosiloxane-based finishing agent comprises thesteps of:

washing and drying a substrate surface;

applying a composition containing a chemical adsorbent, comprising atleast one organosiloxane bond chain and chlorosilyl group, and anonaqueous viscous liquid or a solid medium, to the substrate surface;

reacting and drying the composition; and

wiping off the composition on the substrate surface.

The step of applying the composition and the step of reacting and dryingthe composition are required in this method. It is more efficient toheat the composition to about 50° C. during the reacting and dryingstep. As a result, an overcoat with a high water-separation property canbe formed on the substrate surface.

Conveniently, the organosiloxane-based finishing agent is inhibited fromrunning during application to a substrate surface when the viscosity ofthe viscous liquid or solid medium is 1000 cps or above. If the viscousliquid or solid medium with its boiling point at 200° C. or above ismixed with one having a boiling point from 100° C. to 150° C., anovercoat can firm up quickly right after the application of the agent byvaporizing the material with the low boiling point. As a result, theremoval of the finishing agent simplified.

Moreover, if an abrasive material made of particles less than 10 microns(such as alumina, silicon carbide, boron carbide, chromium oxide, ironoxide, synthetic diamond or fine-grain silica) is added to theorganosiloxane-based finishing agent, a small amount of the substratesurface is removed without reducing the luster of the surface. As aresult, the reaction between chemical admolecules containing at leastone chlorosilyl group and the cleaned substrate surface is improved. Thecontent of this abrasive material in the finishing agent is preferably1-10% by weight.

Examples of a substrate used for the invention include ones havinghydroxyl groups (--OH) on their surfaces--metals such as Al, Cu,stainless steel or the like, glass, ceramics, paper, fiber, leather orother hydrophilic groups. When a material which does not have a hydroxylgroup on its surface such as plastic is used, hyroxyl groups can beintroduced to the surface by a corona treatment of 100W for 20 minutesin a plasma atmosphere containing oxygen, thus making the surfacehydrophilic. However, if a polyamide and polyurethane resin having iminogroups (>NH) on their surfaces is used, such treatment is not necessary;a dehydrochlorination reaction is promoted between the hydrogens of theimino groups (>NH) of the substrate and the chlorosilyl groups (--SiCl)of the chemical admolecule, thereby forming silicon-nitrogen bonds(--SiN--). In the method of forming an overcoat with a highwater-separation property from the organosiloxane-based finishing agent,an adhesive, thin overcoat can be formed on a substrate surface. Sincethe overcoat can be applied any parts where water drops may stick, suchas the sidings and windows of vehicles, the walls and windows ofbuildings, walls, or the like, the overcoat can be significantly useful.

The content of the chemical adsorbent comprising at least oneorganosiloxane bond chain and chlorosilyl group in the finishing agentis preferably 1-30% by weight.

Moreover, any nonaqueous organic material which is inactive to thechemical adsorbent comprising an organosiloxane bond chain andchlorosilyl group can be used as the nonaqueous viscous liquid or solidmedium. Petroleum-based solvents, silicone, paraffin based wax or thelike are especially cheap and useful. More specifically, examples of theorganic solvent include petroleum naphtha, solvent naphtha, petroleumether, petroleum benzene, isoparaffin, N-paraffin, decalin, industrialgasoline, kerosene, ligroin, dimethylsilicone, phenylsilicone, alkylmodified silicone, polyether silicone, paraffin wax, microcrystal wax,polyethylene wax, ester wax, wax, oxide, and petroleum wax. Theabove-noted examples, alone or in combination can be applied as theviscous liquid or solid medium in the invention. The content of theviscous liquid or medium in the finishing agent is preferably 50-90% byweight.

When the organosiloxane based finishing agent of the invention is usedto treat a substrate surface, a thin, oil-repellent and durable overcoatwith a high water-separation property is easily formed on the surface.The procedure for coating the agent on the substrate surface are simple,and does not require a large-scale reactor.

Since the nonaqueous viscous liquid or solid medium is dehydrated to 10ppm of water or less, the chemical adsorbent with at least oneorganosiloxane bond chain and chlorosilyl group which is instable towater can be contained in the organosiloxane-based finishing agent in anactive condition.

In a method of using the organosiloxane-based finishing agent of theinvention, the agent, comprising a chemical adsorbent with at least oneorganosiloxane bond chain and chlorosilyl group and a nonaqueous viscousliquid or solid medium, is applied to a substrate surface comprisinghydrophilic groups. Thus, the chemical adsorbent reacts with thesubstrate surface at room temperature (or a temperature lower than 100°C.), and then the agent is dried. When the substrate surface comprisesactive hydrogens, a dehydrochlorination reaction between the activehydrogens and the chlorosilyl groups is generated. As a result, thechemical adsorbent comprising at least one organosiloxane bond chain andchlorosilyl group is covalently bonded to the substrate surface via Siatoms. Unreacted finishing agent is then either wiped off or washed awaywith detergent or water.

Although the chemical adsorbent is very reactive to moisture in the air,the nonaqueous viscous liquid or solid medium can protect the substratesurface from moisture, thereby helping to promote thedehydrochlorination reaction on the surface. If the finishing agentcontains a solvent having a boiling point of around 200° C.±50° C., thesolvent can be evaporated at a preferable level, thus promoting thereaction between water and the chlorosilyl groups and generating HClsmoothly. As a result, the chemical adsorbent comprising at least oneorganosiloxane bond chain and chlorosilyl group is covalently bonded toa substrate surface via Si atoms, thus forming a ultra thinorganosiloxane-based overcoat with a high water-separation property onthe surface.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a substrate surface, enlarged to amolecular level, explaining the procedures of a surface finishingtreatment of an example according to the invention.

FIG. 2 is a cross-sectional view of a substrate surface of the example,enlarged to a molecular level, coated with a finishing agent of theexample.

FIG. 3 is a cross-sectional view of a substrate surface of the example,enlarged to a molecular level, to which a finishing agent of theinvention is chemically adsorbed.

FIG. 4 is a cross-sectional view of a substrate surface, enlarged to amolecular level, explaining the procedures of a surface finishingtreatment of another example of the invention.

FIG. 5 is a cross-sectional view of a substrate surface, enlarged to amolecular level, explaining the procedures of a surface finishingtreatment of another example of the invention.

FIG. 6 is a cross-sectional view of a substrate surface of anotherexample, enlarged to a molecular level, coated with a finishing agent ofthe invention.

FIG. 7 is a cross-sectional view of a substrate surface of anotherexample, enlarged to a molecular level, coated with a finishing agent ofthe invention.

DETAILED DESCRIPTION OF THE INVENTION

A finishing agent of the invention is mainly comprised of a siloxanecompound, a chemically adsorptive compound with at least one halosilylgroup, tertiary amine or amide containing no active hydrogens, and anonaqueous viscous liquid or solid medium.

Suitable chemical admolecules, containing at least one halosilyl group,include a hydrocarbon-based molecule such as those shown below:

    CH.sub.3 (CH.sub.2).sub.r SiX.sub.p Cl.sub.3-p ;

    CH.sub.3 (CH.sub.2).sub.s O(CH.sub.2).sub.t SiX.sub.p Cl.sub.3-p ;

    CH.sub.3 (CH.sub.2).sub.u Si(CH.sub.3).sub.2 (CH.sub.2).sub.v SiX.sub.p Cl.sub.3-p ;

    CF.sub.3 COO(CH.sub.2).sub.w SiX.sub.p Cl.sub.3-p ;

    Cl.sub.3-p SiX.sub.p (R).sub.m (CF.sub.2).sub.n (R).sub.m SiX.sub.p Cl.sub.3-p ;

    CF.sub.3 (CF.sub.2).sub.n (R).sub.m SiX.sub.p Cl.sub.3-p

wherein r is 1 to 25; s is 0 to 12; t is 1 to 20; u is 0 to 12; v is 1to 20; w is 1 to 25; n is 0 or an integer; R represents an alkyl group,a vinyl group, an ethynyl group, an aryl group or a substituentcomprising a silicon atom or an oxygen atom; m is 0 or 1; X representsH, an alkyl group, an alkoxyl group or a substituent comprising afluoroalkyl group or a fluoroalkoxy group; and p is 0, 1 or 2.

In addition, specific examples of the chemically adsorptive compoundsinclude the following:

    CH.sub.3 CH.sub.2 O(CH.sub.2).sub.15 SiCl.sub.3 ;

    CH.sub.3 (CH.sub.2).sub.2 Si(CH.sub.3).sub.2 (CH.sub.2).sub.15 SiCl.sub.3 ;

    CH.sub.3 (CH.sub.2).sub.6 Si(CH.sub.3).sub.2 (CH.sub.2).sub.9 SiCl.sub.3 ;

    CH.sub.3 COO(CH.sub.2).sub.15 SiCl.sub.3 ;

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3 ;

    Cl.sub.3 Si(CH.sub.2).sub.2 (CF.sub.2).sub.6 (CH.sub.2).sub.2 SiCl.sub.3 ;

    CF.sub.3 (CF.sub.2).sub.5 (CH.sub.2).sub.2 SiCl.sub.3 ;

    CF.sub.3 (CF.sub.2).sub.7 C.sub.6 II.sub.6 SiCl.sub.3.

Tertiary amines or amides with no active hydrogens includetriethylamine, trimethylamine, pyridine, N-methylpyrrolidinon,N-methylpyrrole, N/N-dimethylaniline, triazine, dimethylbutylamine,dipyridine, indole, N/N-dimethylnaphthylamine or the like. The contentof the amine or amide in the finishing agent is more than the amount ofhydrochloric acid, made from the decomposition of the materialcontaining many chlorosilysilyl groups and the molecules comprising atleast one chlorosilyl group, in moles. More specifically, when achemical admolecule comprises one chlorosilyl group, the content shouldbe the same as that of the admolecule in moles. If the chemicaladmolecule comprises two chlorosilyl groups, the content of the amine oramide should be twice as much as that of the admolecule in moles. Thecontent of the amine or amide in the agent should be also three timesmore than that of the admolecule comprising three chlorosilyl groups.However, it is believed that no problems would arise even if the amountof added amine or amide is excessive. It is preferable that the contentof the chemical admolecules in the finishing agent of the invention is1-30% by weight.

Moreover, any nonaqueous solvent having no active hydrogens can be usedas the nonaqueous viscous liquid or solid medium. Petroleum-basedsolvents, silicone, paraffin-based wax or the like are especially cheapand useful.

Examples of such solvents include:

petroleum naphtha; solvent naphtha; petroleum ether; petroleum benzene;isoparaffin; N-paraffin; decalin; industrial gasoline; kerosene;ligroin; dimethylsilicone; phenylsilicone; alkyl modified silicone;polyether silicone; paraffin wax; microcrystal wax; polyethylene wax;ester wax; wax oxide; and petroleum wax.

The above-noted examples, alone or in combination can be applied as theviscous liquid or solid medium in the invention. The content of theliquid or medium in the finishing agent is preferably 50 to 90% byweight.

When the viscosity of the liquid or medium is 1000 cps or above, thefinishing agent does not run, which facilitates handling of the agent.However, it is difficult to handle the agent if the liquid or medium istoo firm. The removal of unreacted agent is simple if the viscous liquidor solid medium with its boiling point at 100° C. or above is mixed withthe one having a boiling point from room temperature to 110° C.

Moreover, if an abrasive material around several microns in diameter(such as alumina, silicon carbide, boron carbide, chromium oxide, ironoxide, synthetic diamond or fine-grain silica), is added to thefinishing agent, a small amount of substrate surface would be removedduring the application of the agent. As a result, the reaction of thechemical admolecules to the substrate is generated easily. The contentof the abrasive material in the agent is preferably 1 to 10% by weight.

A method of manufacturing the finishing agent of the invention comprisesthe steps of:

preparing a nonaqueous viscous liquid or a solid medium:

mixing a tertiary amine or amide with no active hydrogens in the liquidor medium;

mixing a silyl compound comprising at least two halogen groups, thuspromoting the reaction between water contained in the liquid or mediumand the silyl compound so as to form a polysiloxane compound; and

adding and mixing a chemically adsorptive compound comprising at leastone chlorosilyl group with the polysiloxane compound.

It is preferable to use at least one compound selected from the groupconsisting of SiCl₄, SiHCl₃, SiH₂ Cl₂, and SiCl₃ O(SiCl₂ O)_(n) SiCl₃(wherein n represents 0 or an integer) as the silyl compound comprisingmany halogen groups.

Any chlorosilane-based surface active agents, in which straight chainsiloxane bonds are contained and chlorosilane groups (SiCl_(n) X_(3-n),wherein n represents 1, 2 or 3, and X represents a functional group) arebonded at one end of the siloxane bonds, can be used for forming anorganosiloxane-based overcoat with a high water-separation property.However, it is most preferable to use a chemical adsorbent comprising atleast one organosiloxane bond chain and chlorosilyl group, such asR(SiR₂ O)_(m) SiCl_(n) X_(3-n) (wherein m represents an integer,preferably 2-5, n represents 1, 2 or 3, X represents a functional group,and R represents an alkyl group). A functional group includes an alkylgroup or the like.

It is possible to use any chlorosilane-based surface active agent,comprising straight chain siloxane bonds with chlorosilane groups(SiCl_(n) X_(3-n) groups, wherein n represents 1, 2 or 3, and Xrepresents a functional group) at both end of the siloxane bonds, forforming an organosiloxane-based overcoat with a high water-separationproperty. Particularly, it is most preferable to use Cl(SiR₂ O)_(n) SiR₂Cl or Cl₃ SiO(SiR₂ O)_(n) SiCl₃ (wherein R represents an alkyl group,and n represents an integer, preferably 2-5).

However, if the organosiloxane-based finishing agent contains not onlythe material comprising an organosiloxane bond chain and chlorosilylgroup but a material comprising a siloxane bond chain and fluorocarbongroup, an overcoat formed from the finishing agent has a highwater-separation property as well as an oil-repellent property. Thematerial comprising an organosiloxane bond chain and chlorosilyl groupincludes R(SiR₂ O)_(n) SiCl₃ (wherein R represents an alkyl group and nrepresents an integer). Cl(SiR₂ O)_(n) SiR₂ Cl and Cl₃ SiO(SiR₂ O)_(n)SiCl₃ (wherein R represents an alkyl group and n represents an integer).The material comprising a fluorocarbon chain and chlorosilyl group, inaddition, including CF₃ (CF₂)_(n) (R)_(m) SiX_(p) Cl_(3-p) (wherein mand n represents 0 or an integer, R represents an alkyl group, a vinylgroup, an ethylnyl group, an aryl group or a substituent comprising asilicone or an oxygen atom, X represents H, an alkyl group, an alkoxylgroup or a substituent comprising a fluoroalkyl group or a fluoroalkoxygroup, and p represents 0, 1 or 2).

A method of using the organosiloxane-based finishing agent of theinvention comprises the steps of:

washing a substrate surface having active hydrogens thoroughly;

drying the substrate surface;

applying the finishing agent on the substrate surface;

reacting chlorosilyl compound molecules (chemical admolecules) to theactive hydrogens on the substrate surface (such as hydroxyl groups:--OH) at room temperature, thus causing a dehydrochlorination reactionbetween the chlorosilyl groups and the active hydrogens;

covalently bonding the admolecules to the substrate surface via Siatoms; and

wiping off or washing away the extra agent left on the substrate surfacewith detergent or water.

In the above procedure, the admolecules fixed on the substrate surfaceare likely to react to moisture in the air. A nonaqueous viscous liquidor solid medium, however, would protect the substrate from moisture,thereby helping to promote the dehydrochlorination reaction.

After the above-noted steps, chemical admolecules comprising at leastone chlorosilyl group are fixed to the substrate surface by a covalentbonding via Si atoms, thereby forming an ultra thin overcoat at athickness at the angstrom or nanometer level.

Examples of a substrate used for the invention include substrates havinghydroxyl groups (--OH) on their surfaces--metals such Al, Cu, stainlesssteel or the like, glass, ceramics, paper, fiber, leather or otherhydrophilic groups. When a material, such as plastic, does not have ahydroxyl group on its surface, the hydroxyl groups can be introduced tothe surface by a corona treatment of 100 W for 20 minutes in a plasmaatmosphere containing oxygen, thus making the surface hydrophilic.However, when using polyamide and polyurethane resin having imino groups(>NH) on their surfaces, such treatment is not necessary; adehydrochlorination reaction is promoted between the hydrogens of theimino groups (>NH) of the substrate and the chlorosilyl groups (--SiCl)of the chemical admolecule, thereby forming silicon-nitrogen bonds(--SiN--). By fixing an ultra thin fluorocarbon-based polymer overcoatto a substrate surface, numerous applications present themselves,including electric goods such as a hot plate, rice steamer or the like,automobiles, industrial equipment, glass, mirrors, lenses for glasses,interior goods, apparel or the like. The quality of the substrate isalso improved with regard to heat and weather resistance and abrasionproperties.

This invention can be applicable for various uses and materials such asdescribed below.

(a) substrates metal, ceramics, plastic, wood, stone (the inventionbeing applicable even when the substrate surface is coated with paint orthe like in advance):

(b) cutlery--kitchen and other knives, scissors, engraver, razor blade,hair clippers, saw, plane, chisel, gimlet, badkin, cutting tools, drilltip, blender blade, juicer blade, flour mill blade, lawn mower blade,punch, straw cutter, stapler, blade for can opener, surgical knife orthe like;

(c) needles--acupuncture needle, sewing needle, sewing-machine needle,long thick needle for making tatami, syringe needle, surgical needle,safety pin or the like;

(d) products in the pottery industry--products made of pottery, glass,ceramics or enameled products, including hygienic potteries (such aschamber pot, wash-bowl, bathtub, etc.), tableware (such as a rice bowl,plate, bowl, teacup, glass, bottle, coffee-pot, pots and pans,earthenware mortar, cup, etc.), flower vases (such as a flower bowl,flowerpot, small flower vase, etc.), chemistry apparatus (such as abeaker, reacter vessel, test tube, flask, culture dish, condenser,stirring rod, stirrer, mortar, vat, syringe), roof tile, tile, enameledtableware, enameled wash bowl, and enameled pots and pans;

(e) mirrors--hand mirror, full-length mirror, bathroom mirror, washroommirror, mirrors for automobile (back and side mirrors), half mirror,mirror for show window, mirrors for department store or the like;

(f) molding parts--die for press molding, die for cast molding, die forinjection molding, die for transfer molding, die for vacuum molding, diefor blow forming, die for extrusion molding, die for inflation molding,die for fiber spinning, calender processing roll;

(g) ornaments--watch, jewelry, pearl, sapphire, ruby, emerald, garnet,cat's-eye, diamond, topaz, bloodstone, aquamarine, turquoise, agate,marble, amethyst, cameo, opal, crystal, glass, ring, bracelet, brooch,tiepin, earrings, necklace, glasses frames (of patinum, gold, silver,aluminum, titanium, tin, compound metals of these elements, or stainlesssteel) or the like;

(h) molds for food--cake mold, cookie mold, bread mold, chocolate mold,jelly mold, ice cream mold, oven plate, ice tray or the like;

(i) cookware--pots and pans, iron pot, kettle, pot, frying pan, hotplate, net for grilling food, tool for draining off oil, plate formaking takoyaki or the like;

(j) paper--photogravure paper, water and oil repellent paper, paper forposter, high-quality paper for pamphlets or the like;

(k) resin--polyolefin (such as polypropylene, polyethylene, etc.),polyvinylchloride, polyvinylidenechloride, polyamide, polyimide,polyamideimide, polyester, aromatic polyester, polystyrene, polysulfone,polyethersulfone, polyphenylenesulfide, phenolic resin, furan resin,urea resin, epoxide, polyurethane, silicon resin, ABS resin, methacrylicresin, ethylacrylate resin, ester resin, polyacetal, polyphenyleneoxideor the like;

(l) household electric goods--television, radio, tape recorder, audiogoods, CD player, refrigerator, freezer, air conditioner, juicer,blender, blade of an electric fan, lighting equipment, dial plate, hairdrier for perm or the like;

(m) sporting goods--skis, fishing rod, pole for pole vault, boat,sailboat, jet skis, surfboard, golf ball, bowling ball, fishing line,fishing net, fishing float or the like;

(n) vehicle parts;

(1) ABS resin--lamp cover, instrument panel, trimming parts, andprotector for a motorcycle,

(2) cellulose plastic--markings for automobile, and steering wheel,

(3) FRP (Fiber Reinforced Plastics)--bumper, and engine cover,

(4) phenolic resin--brake,

(5) polyacetal--wiper, wiper gear, gas valve, carburetor parts.

(6) polyamide--radiator fan,

(7) polyarylate (polycondensation polymerization by bisphenol A andpseudo phthalic acid)--direction indicator lamp (or lens), cowl boardlens, relay case.

(8) polybutylene terephthalate--rear end, front fender,

(9) poly amino-bismaleimide--engine parts, gear box, wheel, suspensiondrive system.

(10) methacrylate resin--lamp cover lens, meter panel and cover, andcenter mark,

(11) polypropylene--bumper,

(12) polyphenylene oxide--radiator grill, wheel cap,

(13) polyurethane--bumper, fender, instrument panel, and fan,

(14) unsaturated polyester resin--body, gas tank, heater housing, meterpanel,

(o) stationary goods--fountain pen, ballpoint pen, mechanical pencil,pencil case, binder, desk, chair, book shelf, rack, telephone base,ruler, draftsman's outfit or the like;

(p) building materials--roof materials (such as ceramic tile, slate, tinsuch as used in galvanized iron plate, etc.), outer wall materials (suchas wood including processed wood, mortar, concrete, ceramic sizing,metallic sizing, brick, building stone, plastic material, metallicmaterial including aluminum, etc.), interior materials (such as woodincluding processed wood, metallic material including aluminum, plasticmaterial, paper, fiber, etc.) or the like;

(q) stone materials--granite, marble or the like, used for building,building material, works of art, ornament, bath, gravestone, monument,gatepost, stone wall, sidewalk, paving stone, etc.

(r) musical instruments and audio apparatus--percussion instruments,string instruments, keyboard instruments, woodwind instruments, brassinstruments or the like, more specifically, drum, cymbals, violin,cello, guitar, koto, piano, flute, clarinet, shakuhachi, horn, etc., andmicrophone, speaker, earphone or the like.

(s) others--high voltage insulator with good water, oil andcontamination repelling properties, including thermos bottles, vacuumapparatus, insulator for transmitting electricity, spark plugs or thelike.

The invention will be explained specifically with reference to thefollowing illustrative embodiments.

EXAMPLE 1

Soft solid wax was prepared by the following procedures:

mixing an oil-based solvent, a silicone, a paraffin based wax, a silylcompound comprising many Cl groups and the abrasive material listedbelow in an Erlenmeyer flask;

    ______________________________________                                        (as an oil-based solvent)   30 g                                              n-octane (bp. 143° C.)                                                 (as a silicone)             20 g                                              silicone oil (Shinetsu Kagaku Kogyu KF-90, 1000 cps)                          (as a paraffin based wax)   20 g                                              paraffin (made by Kanto mp 84-85° C.)                                  (as a silyl compound comprising many chlor groups)                                                         4 g                                              SiCl.sub.3 OSiCl.sub.3                                                        (as an abrasive material)    5 g                                              alpha-alumina (1 μm in average diameter)                                   ______________________________________                                    

stirring the mixed material at 90° C., thus providing a suspension;

mixing 6 g heptadecafluorodecyl trichlorosilane (CF₃ (CF₂)₇ (CH₂)₂SiCl₃) into the Erlenmeyer flask, as molecules comprising at least onechlorosilyl group; and

cooling the suspension to room temperature.

The wax obtained from the above-noted procedures is used as a finishingagent for the following treatments in order to evaluate the water andoil-repelling property and also endurance.

An ultra thin fluorocarbon polymer overcoat was formed by the followingprocedures:

preparing an automobile window glass 1 (see FIG. 1) with its surfacecomprising numerous active hydrogens (OH groups 2) as a substrate;

applying the prepared finishing agent to the substrate surface with asponge;

letting the substrate sit for 20 to 30 minutes, thus vaporizing n-decaneand forming a white overcoat:

contacting heptadecaflourodecyl trichlorosilane to OH groups 2 to thesubstrate surface at a certain probability, thereby reacting andcovalently bonding heptadecafluorodecyl trichlorosilane molecules 3 tothe substrate surface via SiO bonding by a dehydrochlorination reactionbetween the chlorosilyl groups of the molecules and the active hydrogensof OH groups 2 (FIG. 2).

wiping off the extra agent with a dustcloth, thereby forming an ultrathin fluorocarbon overcoat 4 with a thickness of dozens of angstroms onthe substrate surface by covalently bonding numerousheptadecafluorodecyl trichlorosilane molecules shown in FIG. 3 to thesurface via a network bonding of SiO.

After the above noted procedures, furthermore, the heptadecafluorodecyltrichlorosilane molecule can react with moisture in the air; however, anonaqueous viscous liquid or solid medium, such as silicon oil andparaffin, can prevent the moisture from disturbing the hydrochlorinationreaction on the substrate surface.

The overcoat was not peeled off by a cross cut adhesion test. Thecontact angle of water was 116°. Oil applied on the substrate surfacewas easily wiped off with tissue paper.

EXAMPLE 2

A finishing agent, a mixture of the materials shown below, was preparedand evaluated as in Example 1.

    ______________________________________                                        n-octone (bp. 126° C.)                                                                             20 g                                              n-decone (bp. 143° C.)                                                                             30 g                                              silicone oil (Shinetsti Kagaku Kogyo, KF-96 1000 cps)                                                     20 g                                              paraffin (made by Kanto Kagaku mp. 54-56° C.)                                                      20 g                                              SiCl.sub.3 OSiCl.sub.2 OSiCl.sub.3                                                                         4 g                                              n-methylpyrrolidine          3 g                                              alpha-alumina (1 micron)     5 g                                              ______________________________________                                    

After mixing these materials in an Erlenmeyer flask 7 gheptadecafluorodecyl trichlorosilane (CF₃ (CF₂)₇ (CH₂)₂ SiCl₃) was thenmixed into the flask, thus providing a suspension. The suspension wasthen cooled to room temperature, thus forming a soft solid wax.

Hydrochloric acid was hardly generated when the finishing agent of thisexample was applied on a substrate. The same results as in Example 1were obtained in this example except that a white overcoat was formedafter applying the agent to the substrate surface and letting thesubstrate sit for 10 to 15 minutes. The results are shown in Table 1.

EXAMPLE 3

The same experiment as in Example 2 was conducted in this example exceptthat heptadecafluorodecyl trichlorosilane used in Example 2 was replacedwith tridecafluorooctyl trichlorosilyl (CF₃ (CF₂)₅ (CH₂)₂ SiCl₃). Theresults are shown in Table 1.

EXAMPLE 4

The same experiment as in Example 2 was conducted except that the glassused in Example 2 was replaced with a mirror. The results are shown inTable 1.

EXAMPLE 5

The same experiment as in Example 2 was conducted except that the glassused in Example 2 was replaced with a door of a painted automobile. Theresults are shown in Table 1.

EXAMPLE 6

The same experiment as in Example 2 was conducted except that the glassused in Example 2 was replaced with a hood of an automobile. The resultsare shown in Table 1.

EXAMPLE 7

The same experiment as in Example 2 was conducted except that the alphaalumina used in Example 2 was replaced with silica (1 μm in averagediameter). The results are shown in Table 1.

EXAMPLE 8

The same experiment as in Example 1 was conducted except that the amountof n-decane was changed to 40 g. The viscosity of the prepared liquidwas was about 3000 to 4000 cps. The results are shown in Table 1.

Reference 1

The same experiment as in Example 1 was conducted except that SiCl₃OSiCl₃ was not added to the mixed materials. The results are shown inTable 1.

Reference 2

The same experiment as in Example 2 was conducted except that SiCl₃OSiCl₂ OSiCl₃ was not added to the mixed materials. The results areshown in Table 1.

                  TABLE 1                                                         ______________________________________                                               Contact                                                                       Angle of Water (')                                                                          Contact Angle of Oil (')                                        Initial                                                                              After      Initial  After                                              Number Rubbing Test                                                                             Number   Rubbing Test                                ______________________________________                                        Example 1                                                                              116      115        97     94                                        Example 2                                                                              115      114        95     91                                        Example 3                                                                              113      111        93     92                                        Example 4                                                                              113      112        94     91                                        Example 5                                                                              110      110        94     93                                        Example 6                                                                              111      113        94     92                                        Example 7                                                                              117      108        93     89                                        Example 8                                                                              115      111        93     91                                        Reference 1                                                                             98       95        75     73                                        Reference 2                                                                             93       98        73     69                                        ______________________________________                                    

As clearly seen from Table 1, the substrate treated with a finishingagent of Examples 1-8 maintained its water- and oil-repelling orhydrophilic properties even after the surface was rubbed repeatedly witha wet cloth. In References 1 and 2, however, water- and oil-repellingproperties were low even though the same amount of molecules comprisingat least one chlorosilyl group was added to the mixed materials as theamount added for Examples 1-8.

The method of the invention can efficiently form an overcoat on thesurface of plastic, ceramics, glass, or other materials by forming andfixing a polymer overcoat to the surface comprising active hydrogens.

In the manufacturing method of the invention, the tertiary amine oramide with no active hydrogens is mixed in a prepared nonaqueous viscousliquid or solid medium, and a dehydrochlorination reaction between watercontained in the viscous liquid or solid medium and thiol- oramino-based impurities is promoted by mixing a silyl compound comprisingnumerous chloro groups into the liquid or medium. As a result, apolysiloxane compound is generated, and water and the thiol- oramino-impurities are stabilized as siloxane and hydrochloric acid.Therefore, a chemically adsorptive compound comprising at least onechlorosilyl group which is then added into the mixed materials would notbe deactivated, thus manufacturing an active finishing agent.

If a compound comprising a fluorocarbon and chlorosilyl group is used asa material for forming an overcoat, a highly dense, ultra thin, water-and oil-repelling, anti-contaminating and durable overcoat with auniform thickness can be formed on a substrate including metals, such asAl, Cu, stainless steel or the like by chemical bonding.

The method of manufacturing a finishing agent of the invention iseffective in that heat, weather and abrasion resistant ultra thinovercoat can be applied for coating electric goods such as a hot plateand rice steamer, plus automobiles, industrial equipment, glass, mirror,lenses for glasses or the like.

EXAMPLE 9

Soft solid organosiloxane-based wax was prepared by the followingprocedures:

mixing an oil-based solvent, a silicone, a paraffin-based wax and anabrasive material mentioned below in an Erlenmeyer flask:

    ______________________________________                                        (as an oil-based solvent)   30 g                                              n-paraffin (bp. 180-210° C.)                                           (as a silicone)             18 g                                              silicone oil (Shinetsu Kagaku Kogyo KF-96, 1000 cps)                          (as a paraffin-based wax)   20 g                                              paraffin (made by Wakou Junyaku, mp 95° C.)                            (as an abrasive material)    5 g                                              alpha-alumina (1 micron)                                                      ______________________________________                                    

stirring the mixed material at 100° C., thus providing a whitesuspension:

mixing 6 g chemical adsorbent comprising at least one organosiloxanebond chain and chlorosilyl group, (CH₃)₃ SiO(Si(CH₃)₂ O)₃ SiCl₃, in theErlenmeyer flask; and

cooling the suspension to room temperature.

A white overcoat was formed by the following procedures:

preparing an automobile window glass 1 (see FIG. 4 (a)) with its surfacecomprising numerous active hydrogens (OH groups 2) as a substrate;

applying the prepared organosiloxane-based finishing agent to thesubstrate surface with a sponge; and

letting the substrate siC for 20 to 30 minutes at room temperature, thusvaporizing n-paraffine and forming a white overcoat.

Covalent bonds shown in the following Formula 1 were formed on theentire surface of the substrate by a dehydrochlorination reactionbetween hydroxyl groups 2 of the substrate surface and the chlorosilyl(--SiCl) groups of the chemical adsorbent. ##STR1##

Then, extra finishing agent was wiped off with a dustcloth, and thechlorosilyl groups left on the substrate surface were reacted withmoisture in the air. As a result, an organosiloxane-based overcoat 5with a thickness of about 10 angstroms was formed on the substratesurface by convalently bonding numerous chemical admolecules as shown inthe following Formula 2 to the surface via a network bonding of SiO(FIG. 5 (b)). The formation of the overcoat was confirmed by a Fouriertransform infrared spectroscopy (FTIR). ##STR2##

Even if silicon oil and paraffin were on the substrate surface and inthe overcoat, a dehydrochlorination reaction between the chlorosilylgroups of the chemical adsorbent and the OH groups of the substratesurface was generated at a certain ratio. As a result, the chemicaladmolecules were covalently bonded to the substrate surface via SiObonds.

The chemical adsorbent can react with moisture in the air: however, anonaqueous viscous liquid or solid medium, such as silicon oil andparaffin, can prevent the moisture from disturbing the hydrochlorinationreaction on the substrate surface.

The substrate formed with the overcoat of the example was washedthoroughly with detergent and water, and then water-repelling properties(contact angle of water) as well as water-separation properties (angleat which a drop of water slides down a substrate surface when thesubstrate is slowly tilted) were measured. The contact angle was 101°while the angle of a sliding 0.08 cc drop of water was 15°. Theoil-repelling property, in addition, was measured by using hexadecane,and the contact angle of oil was 45°.

The film, in addition, was not peeled off by a cross-cut adhesion test.

EXAMPLE 10

Liquid wax was prepared by the following procedures:

mixing the following materials in an Erlenmeyer flask:

    ______________________________________                                        n-octane (bp. 126° C.)                                                                             20 g                                              n-paraffin (bp. 220-240° C.)                                                                       30 g                                              silicone oil (Shinetsu Kagaku Kogyo KF-96, 1000 cps)                                                      20 g                                              paraffin (made by Wakou Junyaku, mp 95° C.)                                                        15 g                                              alpha-alumina (1 micron)     5 g                                              n-methyl pyrrolidine         3 g                                              ______________________________________                                    

mixing 7 g siloxane-based material comprising two chlorosilyl groups atthe ends of molecules, Cl₃ SiO(Si(CH₃)₂ O)₃ SiCl₃, in the Erlenmeyerflask; and

cooling the suspension to room temperature.

A white overcoat was formed by the following procedures:

preparing a rearview mirror 10 (see FIG. 5 (a)) of an automobile withits surface comprising numerous active hydrogens (OH groups 2) as asubstrate;

rubbing the prepared finishing agent on the substrate surface with asponge; and

heating the substrate for 20 to 30 minutes at 50° C., thus vaporizingn-octane and n-paraffine and forming a white overcoat.

A dehydrochlorination reaction between the chlorosilyl (--SiCl) group atone end of a molecule and the hydroxyl groups of the substrate surfacewas generated, thus forming an overcoat shown in the following Formula 3on the entire surface of the substrate. ##STR3##

Then, extra finishing agent on the substrate surface was washed awaywith an organic solvent and then with water. The overcoat shown inFormula 3 was reacted with moisture in the air, thus forming anorganosiloxane-based overcoat 6 shown in the following Formula 4 on thesubstrate surface (FIG. 5 (b)). ##STR4##

Organosiloxane-based overcoat 6 with a thickness of about 10 angstromswas hydrophilic and formed on the substrate surface via a chemicalbonding.

The contact angle of water was 88° while the angle of a sliding 0.08 ccdrop of water was 10°. The oil-repelling property was also measured byusing hexadecane, and the contact angle of oil was 58°.

EXAMPLE 11

The same experiment as in Example 9 was conducted, except that thechemical adsorbent used in Example 9 was replaced with a chemicaladsorbent in which Cl(Si(CH₃)₂ O)₄ SiCl₃ and CF₃ (CH₂)₅ SiCl₃ were mixedat a mole ratio of 1:1.

Since two kinds of materials containing many chlorosilyl (--SiCl) groupsat the ends of molecules were used as the chemical adsorbent of thisexample, an overcoat in which molecules shown in the following Formulas5 and 6 were mixed was formed. The formation of the overcoat wasconfirmed by FTIR. ##STR5##

In other words, due to a dehydrochlorination reaction between thehydroxyl groups on the substrate surface and the SiCl groups, anovercoat 7 in which a material containing fluorocarbon groups and asiloxane-based material were mixed was chemically bonded to thesubstrate surface (FIG. 6).

The contact angle of water on overcoat 7 was 103° while the angle of asliding 0.08 cc drop of water was 8°. Oil-repelling property was alsoobserved by using a hexadecane, and the contact angle of oil was 70°.

EXAMPLE 12

The same experiment as in Example 10 was directed, except that thechemical adsorbent was replaced with a chemical adsorbent, Cl(Si(CH₃)₂O)₃ SiCl₃, mentioned in Example 10 and CF₃ CF₂ (CH₂)₂ SiCl₃ ; they weremixed at a mole ratio of 4:1.

Since two kinds of materials containing many chlorosilyl (--SiCl) groupsat the ends of molecules were mixed in the finishing agent, an overcoatin which molecules as shown in Formulas 7 and 8 were mixed was formed onthe substrate surface. The formation of the overcoat was found by FTIR.##STR6##

More specifically, due to a dehydrochlorination reaction between theSiCl groups and the hydroxyl groups on the substrate surface, anovercoat 8 in which a material containing fluorocarbon groups and asiloxane-based material were mixed was chemically bonded to thesubstrate surface (FIG. 7).

The contact angle of water on overcoat 8 was 96° while the angle of asliding 0.08 cc drop of water was 5°. The oil-repelling property ofovercoat 8 was also observed by using hexadecane, and the contact angleof oil was 68°.

Reference 3

The same materials as in Example 9 were used except that (CH₃)₃SiO(Si(CH₃)₂ O)₃ SiCl₃ used in Example 9 was replaced with CF₃ (CF₂)₇(CH₂)₂ SiCl₃. Then, the same experiment as in Example 9 was conductedexcept that the window glass substrate used in Example 9 was replacedwith a slide glass. The contact angle of water as well as the angle of asliding drop of water are shown in Table 2. The oil-repelling propertyof an overcoat formed from the finishing agent of this example wasobserved by using hexadecane, and the contact angle of oil was 75°.

Reference 4

The same materials as in Example 12 were used except that Cl(Si(CH₃)₂O)₃ SiCl₃ was not added to the materials in this reference. Then, thesame experiment as in Example 12 was conducted except that mirrorsubstrate used in Example 12 was replaced with a slide glass. Thecontact angle of water as well as the angle of a sliding drop of waterare shown in the following table 2. The oil-repelling properties of anovercoat formed from the finishing agent of this example were observedby using hexadecane, and the contact angle of oil was 72°.

                  TABLE 2                                                         ______________________________________                                               Contact Angle of Water (')                                                                    Angle of Sliding* (')                                         Initial  After      Initial  After                                            Number   Washing    Number   Washing                                   ______________________________________                                        Example 9                                                                              106        105        13     12                                      Example 10                                                                              83         85        10      7                                      Example 11                                                                              96         98         7      8                                      Example 12                                                                              96         96         8      6                                      Reference 3                                                                            113        114        24     26                                      Reference 4                                                                            108        107        21     22                                      ______________________________________                                         *Angle of a Sliding Drop of Water (Showing A Waterseparation Property)   

As seen from Table 2, the substrate treated with the finishing agents ofExamples 9-12 and References 3-4 maintained its water- and oil-repellingproperties even after the surface was rubbed and washed with a clothcontaining detergent. Finishing agents of Examples 9-12 comprisingsiloxane bond chains provided smaller contact angles of water comparedwith the finishing agents of References 3 and 4. However, theseorganosiloxane-based agents of Examples 9-12 can provide significantlysmall angles of a sliding drop of water while the agents of References 3and 4 have large angles of sliding. Therefore, the organosiloxane-basedfinishing agents of the invention can provide a high water-separationproperty.

The chemical adsorbents comprising an organosiloxane bond chain and manychlorosilyl groups at the ends of molecules mentioned in the examplesdescribed above include the following:

    (CH.sub.3).sub.3 SiO(Si(CH.sub.3).sub.2 O).sub.3 SiCl.sub.3 ;

    Cl.sub.3 SiO(Si(CH.sub.3).sub.2 O).sub.3 SiCl.sub.3 ;

    Cl(Si(CH.sub.3).sub.2 O).sub.4 SiCl.sub.3 ;

    CF.sub.3 (CH.sub.2).sub.3 SiCl.sub.3 ;

    Cl(Si(CH.sub.3).sub.2 O).sub.3 SiCl.sub.3 ; and

    CF.sub.3 CF.sub.2 (CH.sub.2).sub.5 SiCl.sub.3.

The following chemical adsorbents or a mixture of these adsorbents canalso be used in the invention:

    (CH.sub.3).sub.3 SiOSi(CH.sub.3).sub.2 OSiCl.sub.3 ;

    (CH.sub.3).sub.3 SiO(Si(CH.sub.3).sub.2 O).sub.2 SiCl.sub.3 ;

    (CH.sub.3).sub.3 SiO(Si(CH.sub.3).sub.2 O).sub.4 SiCl.sub.3 ;

    (CH.sub.3).sub.3 SiO(Si(CH.sub.3).sub.2 O).sub.5 SiCl.sub.3 ;

    Cl.sub.3 SiOSi(CH.sub.3).sub.2 OSiCl.sub.3 ;

    Cl.sub.3 SiO(Si(CH.sub.3).sub.2 O).sub.2 SiCl.sub.3 ;

    Cl.sub.3 SiO(Si(CH.sub.3).sub.2 O).sub.4 SiCl.sub.3 ;

    Cl.sub.3 SiO(Si(CH.sub.3).sub.2 O).sub.5 SiCl.sub.3 ;

    Cl(Si(CH.sub.3).sub.2 O).sub.2 SiCl.sub.3 ;

    Cl(Si(CH.sub.3).sub.2 O).sub.5 Si(Cl).sub.3 ;

    ClSi(CH.sub.3).sub.2 OSi(CH.sub.3).sub.2 Cl;

    Cl(Si(CH.sub.3).sub.2 O).sub.2 Si(CH.sub.3).sub.2 Cl;

    Cl(Si(CH.sub.3).sub.2 O).sub.3 Si(CH.sub.3).sub.2 Cl;

    Cl(Si(CH.sub.3).sub.2 O).sub.4 Si(CH.sub.3).sub.2 Cl;

    Cl(Si(CH.sub.3).sub.2 O).sub.5 Si(CH.sub.3).sub.2 Cl;

    Cl.sub.3 Si(CH.sub.2).sub.2 (CF.sub.2).sub.6 (CH.sub.2).sub.2 SiCl.sub.3 ;

    CF.sub.3 (CH.sub.2).sub.2 SiCl.sub.3 ;

    CF.sub.3 (CH.sub.2).sub.3 SiCl.sub.3 ;

    CF.sub.3 CF.sub.2 (CH.sub.2).sub.2 SiCl.sub.3 ;

    CF.sub.3 CF.sub.2 (CH.sub.2).sub.3 SiCl.sub.3 ;

    CF.sub.3 CF.sub.2 (CH.sub.2).sub.5 SiCl.sub.3 ;

    CF.sub.3 (CF.sub.2).sub.2 (CH.sub.2).sub.2 SiCl.sub.3 ;

    CF.sub.3 (CF.sub.2).sub.3 (CH.sub.2).sub.2 SiCl.sub.3 ;

    CF.sub.3 (CF.sub.2).sub.3 (CH.sub.2).sub.8 SiCl.sub.3 ;

    (CH.sub.3).sub.3 Si(CH.sub.2).sub.10 SiCl.sub.3 ;

    CH.sub.3 (CH.sub.2).sub.10 SiCl.sub.3 ;

    Cl.sub.3 Si(CH.sub.2).sub.8 SiCl.sub.3 ; and

    Br(CH.sub.2).sub.14 SiCl.sub.3.

Triethylamine, trimethylamine, pyridine, N-methylpyrrolidinon,N-methylpyrrole, N/N-dimethylaniline, triazine, dimethylbutylamine,dipyridine, indole, N/N-dimethylnaphthylamine or the like are suitableas the tertiary amine or amide with no active hydrogens. The content ofthe amine or amide in a finishing agent is greater than the amount ofhydrochloric acid, made from the decomposition of the materialcontaining many chlorosilysilyl groups and the molecules comprising atleast one chlorosilyl group in moles. More specifically, with a chemicaladmolecule comprising one chlorosilyl group, the content should be thesame as that of the admolecule in moles. If the chemical admoleculecomprises two chlorosilyl groups, the content of the amine or amideshould be twice as much as that of the admolecule in moles. The contentof the amine or amide in the agent should be also three times greaterthan that of the admolecule comprising three chlorosilyl groups.However, it is believed that no problems will arise even if the amountof added amine or amide is excessive.

If a chemical adsorbent--in which a material comprising anorganosiloxane bond chain and chlorosilyl group and a materialcomprising a fluorocarbon chain and chlorosilyl group are mixed--is usedto form an overcoat, an overcoat with a high water-separation propertyand an oil-repellent property can be formed on various materialsefficiently.

This overcoat having a high water-separation property is effective inthat it can be applied to a substrate requiring an anti-heat, -weatherand -abrasion ultra thin film with a high water-separation property suchas electric goods, automobiles, industrial equipment, glasses, mirrorsor the like.

The invention may be embodied in other specific forms without departingfrom the spirit or essential characteristics thereof. The embodimentsdisclosed in this application are to be considered in all respects asillustrative and not restrictive, the scope of the invention beingindicated by the appended claims rather than by the foregoingdescription, and all changes which come within the meaning and range ofequivalency of the claims are intended to be embraced therein.

I claim:
 1. A finishing agent comprising a siloxane compound, selectedfrom the group consisting of Si(OH)₄, SiH(OH)₃, SiH₂ (OH)₂, and Si(OH)₃O[Si(OH)₂ O]_(n) Si(OH)₃, wherein n represents 0 or an integer, achemically adsorptive compound comprising at least one halosilyl group,and a nonaqueous viscous liquid or solid medium having a viscosity of1000 cps or above.
 2. A finishing agent according to claim 1, whereinthe chemically adsorptive compound comprising at least one halosilylgroup is represented by the formula ASiX_(p) Y_(3-p), wherein Arepresents an organic group selected from the group consisting of analkyl group, a vinyl group, an ethynyl group, an aryl group a siliconcontaining organic group and an oxygen containing organic group, X is amember selected from the group consisting of H, an alkyl group, analkoxyl group, a fluoroalkyl group and a fluoroalkoxyl group, Yrepresents at least one halogen group selected from the group consistingof Cl, Br, F and I, and p represents 0, 1 or
 2. 3. A finishing agentaccording to claim 1, wherein the nonaqueous viscous liquid or solidmedium has a boiling point of 100° C. or above and is mixed with anothernonaqueous viscous liquid or solid medium having a boiling point from25° C. to 100° C.
 4. A finishing agent according to claim 1, whereinfurther comprises inorganic particles smaller than 10 μm in averagediameter.